In English it’s OK to say “I eat (it) while sitting down.” but in Japanese, 座りながら食べる is an ungrammatical sentence. Why? The reason is:
～ながら indicates multitasking, so 2 actions need to continue at the same time. The action of 食べる, to eat, can take a while but the action of 座る, to sit down, takes a second to complete. So it is impossible for these 2 actions to be continued at the same time.
Also, “sitting down” is explaining how the action of eating is done, rather than it is one of the multitasking actions. In that case, it is better to use the てform here.
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